Triglycidyl ether of trihydroxy bisphenyl ester of acrylic acid

ABSTRACT

BISPHENOL-A-BIS(2,3 - DIMETHACRYLATOPROPYL ETHER) AND THE ADDUCT OF METHACRYLIC ACID AND TRIGLYCIDYL ETHER OF TRIHYDROXY BIPHENYL ARE UTILIZED AS BINDERS FOR DENTAL RESTORATIVE COMPOSITIONS.

ed States Patent O1 hc 3,755,420 TRIGLYCIDYL ETHER OF TRIHYDROXY BIS- PHENYL ESTER OF ACRYLIC ACID- Donald G. Stotfey, and Henry L. Lee, Jr., San Marino, Califl, assignors to Lee Pharmaceuticals, South El Monte, Calif.

No Drawing. Original application Dec. 28, 1970, Ser. No. 102,044. Divided and this application July 14, 1972, Ser. No. 271,763

Int. Cl. C07c 69/54 US. Cl. 260-486 R 4 Claims ABSTRACT OF THE DISCLOSURE Bisphenol-A-bis(2,3 dimethacrylatopropyl ether) and the adduct of methacrylic acid and triglycidyl ether of trihydroxy biphenyl are utilized as binders for dental restorative compositions.

This application is a divisional of application Ser. No. 102,044, filed Dec. 28, 1970, now US. Pat. 3,721,644.

3,755,420 Patented Aug. 28, 1973 which is glycidyl methacrylate derivative of bisphenol-A and which is sometimes referred to as BlS-GMA. This compound has also been referred to as bisphenol-A-bis(3- methacrylato-2-hydroxypropy1)ether.

While the general properties of BIS-GMA are quite good for dental restorative purposes, this resin is extremely viscous and sometimes tends to absorb undesirable amounts of water when used in wet environments, and has a gel time longer than that which is desirable for many purposes.

SUMMARY OF THE INVENTION BACKGROUND OF THE INVENTION Field of the invention This invention is related to certain aromatic, thermowherein each of R and R may independently be hydrogen, lower alkyl, i.e., straight or branched chain alkyl of 1 to 4 carbon atoms, methyl being preferred, or halogen, chlorine being preferred; and

setting acrylic resins and their use as binders in dental filling compositions for the direct filling of teeth.

DESCRIPTION OF THE PRIOR ART Thermosetting acrylic esters of bisphenolic compounds have been used in the past for a variety of purposes, including, for example, the potting of electrical coils. Many such compounds are disclosed in US. Pat. 2,890,202.

Certain specific acrylic resins have been used as binders for dental restorative purposes. In particular, the compounds disclosed in Bowen in US. Pat. 3,066,112 and 3,179,623 have been used with some success.

Chief among the resins of Bowen is a compound having the formula:

H II

wherein R is a hydrogen, lower alkyl, i.e., straight or branched chain alkyl of 1 to 4 carbon atoms, preferably methyl, or halogen, chlorine being preferred. The preferred meaning of R is methyl.

DESCRIPTION OF THE PREFERRED EMBODIMENTS As indicated above, in accordance with the present invention, dental restorative compositions having improved handling characteristics, higher crosslinked densities and other favorable characteristics are obtained when a monomeric polyacrylic resin of the present invention is used as the predominant binder component.

The general classes of such monomeric resins have been defined in the above formulae. Two monomer compounds 3 4 falling within the scope of the foregoing formulae are day at 65 C., and an additional day at 80 C. The prodparticularly preferred. First is a compound of the fornet, the compound of Formula II above, is an amber, vismula: cous liquid.

CH3 CH3 (l'lHa cnpd-o-o-onicnom-o-@-h-@-oonisnore-04:43:03, ll 5 e 3 I OH: CHg=(?-C=O O=J'JC|J=CH1 CH: CH3 which may be named bisphenol-A-bis(2,3-dimethacrylato- The product obtained according to Example 1 above propyl ether); and the second is a compound of the forexhibits a significantly lower viscosity than BIS-GMA. mula: This compound and the compound of Example 2 can be i C C i GH=Z(B-O-CH2EHCH;O -OCH2ZHCHg-OC?=CH2 H H: H (I) 3 CH3 H2CHCH -OC(IJ=CH1 H CH; (II) The foregoing monomers yield thermosetting polymers formulated into dental restorative filler compositions of increased crosslinked density over those previously without the use of any viscosity reducing diluents. It is utilized by the prior art. The resins of the present invenespecially significant to note that the compound of Extion have a much faste gel time than the prio a meteample 1 has significantly less water absorption tendencies rials and a generally lower degree of swelling in the po th n BIS-GMA, lymerized material results. An additional advantage of A i di t d, h monomeric polyacrylic resins f thi the compounds of Formul I s that the absehee of y invention are utilized as binders in dental restorative dfoxyl groups lessens the amount Of Water Whlch can he compositions. Typically, such compositions consist of apabsorbed by the material. proximately 65 to 75% by weight of finely divided solid The acrylates of Formula I of this invention y be particles of a filler and about 25 to by weight of a prepared by reacting BIS-GMA with an excess of an acryl resin bi d chloride in the presence of a tertiary amine such as tri- Th filler may b any finely di id d olid hi h when ethylamihe Py dispersed through the binder system will give improved The compounds of Formula in of this invention may 35 structural strength when the binder system is polymerized he P p y reacting the y y ether of Y Y into a cured resin. The finely divided filler may have a biphenyl with methacrylic acid in the presence of a catai l i generally i h range of about 1 micron 1V511 such as a ttertiary amine, p y p p i to about 150 microns. The preferred range is from about triphenylantimony. The former is commercially available 1 micron to 30 microns, Th best results are b i d as P While KOPOX'171 y he used in its 40 where the inorganic filler is treated with a keying agent Commercially available form. it cantaihs a Significant P to improve the bond between the organic polymer binder re of high molecular weight material and undistiland the surfaces of the finely divided filler particles. Keylah e Colored matter, the Presence of which tends to ing agents which have been found highly suitable are the impart undesirable color to the desired acrylate product. ethylenically unsaturated organo flane fi i hi or keying It is preferable that the Kopox-171 be molecularly disagents where h fifl i fu ed ili l l i filled to Yield Substantially P y y ethel' of oxide, or crystalline quartz and the binder system is of hydrox-y biphenyl. the type described. The finely divided filler may be The feliOWiHg examples describing eel'tam specific treated with the keying agent, for example, in the manner bodiments of the invention will serve to further illustrate described in S p 3 066,112 h i an aqueous the nature of t e illvelltionsolution of tris(2-methoxyethoxy) vinyl silane is cata- Example 1 lyzed with sodium hydroxide to give a pH of 9.3 to 9.8,

and the filler treated with this solution, for example,

110 Of freshly distilled metheclyl ehlolide is added one-half percent of the silane being used per weight of dropwise to a SOhltiOh Of 260 2- 0f P fused quartz. A slurry so formed is dried at about 125 methacrylate 2 hydroxypropyl)ether, 440 ml. of dry C and 1 methylene Chloride and 170 of triethylamih- During 05 Although aluminum oxide in the form of fused aluthe addition. the reaction mixture is p at a temperature mina, having a particle size of 10 microns to 50 microns, between 10 and 15 C. Following completion of the addigives excellent Compressive strength, it may not be tion, the temperature of the solution is allowed to warm Sirable to use the Same in preparing anterior dental to room temperature during continuous stirring and mainfillings, as dental fillings using aluminum oxide due to its tained at that temperature for approximately 30 minutes. extreme hardness and abrasive characteristics, m Pick Thereafter amine Salt formed is filtered 0m and the up marks from a metal utensil when rubbed against the remaining cake washed with methylene chloride. The same thus making Such dental fillings, from the stand combined Organic layer is Washed with normal Y' point of appearance, possibly undesirable when such markdrochloric acid until acidic and than with Water umll ings might become visible to a casual observer. However, neutral- After a final wash with it is dried over because of the excellent wear resistance of fillings obanhydrous sodium sulfate and the solvent removed by tamed using fused alumina, such fillings are highly suit evaPoratioh on a W evapol'ifltof at 'f Pres able for filling teeth where any marking, through the sure. The residue is a colorless liquid of significantly less Contact with utensils, is less likely t0 90cm, and if it Viscosity than should occur would not be visibly apparent to the casual Example 2 observer.

Where more translucent filling materials are desired, as 35.5 g. of the triglycidyl ether of trihydroxy biphenyl for the filling of anterior teeth, glass beads, or a mixture (obtained by the molecular distillation of Kopox-17l), of glass beads and quartz may be used.

24 g. of methacrylic acid and 0.6 ml. of triethylamine The resins produced in accordance with Examples 1 are heated for one day at 45 0., one day at 55 0., one and 2 are ready for use without dilution or treatment with a reactive diluent as has been necessary previously. About 0.5 to 1 percent by weight based on the weight of binder, or more, or an activator, such as, for example, dimethyl-para-toluidine, may be added to the resin. A suitable catalyst, such as, for example, 1 percent by weight benzoyl peroxide, based on the weight of binder, may be mixed into the treated filler material. The filler material containing the catalyst and the resin containing the activator may then be thoroughly mixed together and promptly placed in a cavity to be filled. The binder will polymerize at mouth temperature to harden the filling within about ten minutes.

Other suitable activators include, inter alia, para-toluene sulfinic acid, para-tolyl diethanol amine and other tertiary amines which are well known in the art. The amount of activator to be useddepends on the particular compound 6 been silane treated in the manner described above in the proportion of 30% resin and 70% filler by Weight. The resulting composition is placed in the prepared cavity of a tooth, a satisfactory gel forming in approximately 5 2 /2. to 3 minutes. The compressive strength of the filling was 30,000 p.s.i. after 15 minutes, 31,400 p.s.i. after 30 minutes, and 34,700 p.s.i. after 1 hour according to American Dental Association Specification No. 9.

Also, the solubility and disintegration characteristics of the solid fillings, as judged by the same specification, are very low. All other characteristics of the compositions of this invention indicate a high utility as a dental restorative material.

We claim:

1. A compound of the formula:

utilized and on the working time desired. Generally the activator will be present in amounts of less than 1 percent by weight of the monomers in the binder.

While benzoyl peroxide is a preferred catalyst, other peroxide, 0.1% N,N-dimethyl-(p-toluidine). This resin art. The catalyst should preferably be present in an amount ranging from 1 percent to 2 percent by weight based on the weight of the monomers present in the binder.

The solid fillings formed from the compositions of this invention have high compressive strengths which are well within the standards as set forth in American Dental Association Specification No. 9.

By way of illustration, the monomer compound of Example 1 is mixed with one percent by weight of benzoyl peroxide, 0.1% N,N-dimethyl-(p-toluidine). This resin mixture is then blended with a silica filler which has wherein R is hydrogen, lower alkyl, or halogen.

2. A compound as claimed in claim 1 wherein R is hydrogen.

3. A compound as claimed in claim 1 wherein R is lower alkyl.

4. A compound as claimed in claim 1 wherein R is 30 methyl.

References Cited UNITED STATES PATENTS 3,679,447 7/1972 Aronoif et a1. 106-287 FQREIGN PATENTS 657,894 2/1963 Canada 260-486 R LORRAINE A. WEINBERGER, Primary Examiner 40 P. J. KILLOS, Assistant Examiner UNITED STATES PATENT AND TRADEMARK OFFICE QERTIFICATE OF CORRECTION PATENT NO. 3, 755, 420

DATED August 28, 1973 r yE oms) Donald G. Stoffey and Henry L. Lee, Jr.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, formula 1, those portions of the formula reading CH- -CH II should read O I 0 l -C=O Signed and Scaled this twenty-sixth D ay of August 1 9 75 [SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner ufPaIenIs and Trademarks 

